Current-induced dark layer formation for metallization in electronic devices

ABSTRACT

In various embodiments, bilayers are formed in electronic devices at least in part by anodization of metal-alloy base layers.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/873,970, filed Jan. 18, 2018, which claims the benefit of andpriority to U.S. Provisional Patent Application No. 62/448,137, filedJan. 19, 2017, and U.S. Provisional Patent Application No. 62/535,403,filed Jul. 21, 2017, the entire disclosure of each of which is herebyincorporated herein by reference.

TECHNICAL FIELD

In various embodiments, the present invention relates to themetallization of electronic devices such as flat panel displays andtouch panel displays, in particular to capping and barrier layers forsuch metallization.

BACKGROUND

Flat panel displays have rapidly become ubiquitous in various markets,and are now commonly utilized in a variety of appliances, televisions,computers, cellular phones, and other electronic devices. One example ofa commonly used flat panel display is the thin film transistor (TFT)liquid crystal display (LCD), or TFT-LCD. A typical TFT-LCD contains anarray of TFTs each controlling the emission of light from a pixel orsub-pixel of an LCD. FIG. 1 depicts the cross-section of a conventionalTFT 100 as might be found in a TFT-LCD. As shown, the TFT 100 includes agate electrode 105 formed on a glass substrate 110. A gate insulator 115electrically insulates the gate electrode 105 from overlying conductivestructures. An active layer 120, typically composed of amorphoussilicon, conducts charge between a source electrode 125 and a drainelectrode 130, under the electrical control of gate electrode 105, andthe conducted charge controls the operation of the pixel or sub-pixelconnected thereto (not shown). A source/drain insulator 132 electricallyisolates the source electrode 125 from the drain electrode 130 andprotectively seals the TFT 100. As shown, each of the gate electrode105, source electrode 125, and drain electrode 130 typically include abarrier metal layer 135 and a metal conductor layer 140 thereover. Thebarrier 135 provides good adhesion between the conductor 140 and theunderlying glass and/or silicon and reduces or prevents diffusiontherebetween. Although it is not shown in FIG. 1, the TFT 100 may alsoincorporate a capping layer above the conductor 140.

Over time, LCD panel sizes have increased and TFT-based pixel sizes havedecreased, placing increasingly high demands on the conductors withinthe TFT-LCD structure. In order to decrease the resistance in theconductors and thereby increase electrical signal propagation speeds inthe TFT-LCD, manufacturers are now utilizing low-resistivity metals suchas copper (Cu) for the conductors 140 within the display. However,conventional barriers 135 (and capping layers, if present) may stillpresent issues affecting the performance and processing of TFTs. Forexample, such layers may not be stable in corrosive (e.g., high-humidityand/or high-temperature) environments.

Similarly, touch-panel displays are becoming more common in electronicdevices, and they may even be utilized in tandem with TFT-LCDs. Atypical touch-panel display includes an array of sensors arranged inrows and columns and that sense a touch (or close proximity) of, e.g., afinger, via capacitive coupling. FIG. 2A schematically depicts anexemplary sensor array 200 for a touch-panel display that includesmultiple conductive column sensors 210 that are interconnected to formcolumns 220, as well as multiple conductive row sensors 230 that areinterconnected to form rows 240. The sensors 210, 230 are formed over asubstrate 250 and are electrically coupled to a processor 260 that bothsenses the changes in capacitive coupling that represent “touches” andprovides these signals to other electronic components within a device(e.g., a computer or mobile computing device that incorporates a touchscreen). The sensors 210, 230 may be formed of a transparent conductorsuch as indium tin oxide (ITO), and the substrate 250 may be glass orany other suitably rigid (and/or transparent) support material.

FIG. 2B depicts a magnified perspective view of a point within thesensor array 200 where the interconnected column sensors 210 intersectthe interconnected row sensors 230. In order to avoid electricalshorting between the columns 220 and the rows 240 (see FIG. 2A), theinterconnections between column sensors 210 are isolated from theunderlying or overlying row sensors 230. For example, as shown in FIG.2B, an insulator layer 270 is disposed between the column 220 of columnsensors 210 and a conductive interconnect (or “bridge”) 280 thatelectrically connects the row sensors 230 within a row 240. As shown inFIG. 2C, the interconnects 280 are typically composed of an Alconductive layer 290 with an overlying metallic barrier or capping layer295. The capping layer 295 helps to prevent diffusion from theconductive layers 290 and protects conductive layers 290 from corrosionduring processing and product use. The capping layer 295 may alsoimprove adhesion to overlying layers. Although not shown in FIG. 2C, abarrier layer (e.g., as described above) may also be present below theconductive layer 290. However, as described above for TFT-LCDs, themetals conventionally used for the capping layer 295 (and barrierlayers, if present) suffer from one or more deficiencies that limitperformance and/or present difficulties in the fabrication process orduring operation of the device. For example, the capping layers 295 (andbarrier layers) may have high reflectivity and/or be susceptible tochanges in physical and/or optical properties upon exposure to corrosiveor other aggressive environments. Highly reflective capping layers maybe more visible through the touch screen of the final device,deleteriously impacting the visual aesthetics of the device.

In view of the foregoing, there is a need for barrier and/or cappingmetal layers for electronic devices such as TFT-LCDs and touch-paneldisplays that provide low reflectivity and that are stable upon exposureto corrosive environments.

SUMMARY

In accordance with various embodiments of the present invention,electronic devices such as TFT-LCDs and touch-panel displays, and themetallic interconnects and electrodes therein, are fabricated utilizingbilayer capping and/or barrier layers that provide low reflectivity andhigh corrosion resistance. The bilayers include a base layer thatincludes, consists essentially of, or consists of an alloy of Mo and/orCu and one or more anodizable metallic elements (e.g., Ta, Nb, Al, Hf,Zr, Ti, and/or Mg) present collectively at weight concentrations of,e.g., 0.5% to 50%, 0.5% to 20%, or even 0.5% to 10%. (Herein, all dopantconcentrations are by weight unless otherwise indicated.) In variousembodiments, the base layer is anodized to form an overlying dielectriclayer that includes, consists essentially, or consists of an oxideand/or nitride of the anodizable metallic element(s). Since Cu and Moare typically not anodizable, the overlying dielectric layer may besubstantially free of Cu and Mo, i.e., may contain Cu and/or Mo in trace(e.g., detectable via chemical analysis) amounts insufficient to affectthe properties of the layer, e.g., dielectric constant, corrosionresistance, and/or reflectivity. In various embodiments, a layer being“substantially free of” one or more elements means that the layercontains, by weight, less than 1%, less than 0.8%, less than 0.5%, lessthan 0.3%, less than 0.2%, less than 0.1%, less than 0.05%, or less than0.01% of the one or more elements, individually or in combination; oneor more (or even all) of the elements may be present in the layer at afinite, non-zero concentration, e.g., more than 0.001%, more than0.005%, more than 0.01%, more than 0.05%, more than 0.1%, or more than0.5%. In addition, an interfacial region of the base layer (i.e., theportion of the base layer directly underlying and in contact with thedielectric layer) may be depleted in, or may even be substantially freeof, the anodizable metallic element(s), which may be preferentially“consumed” in the anodizing process.

Advantageously, the resulting bilayers have lower reflectivity andimproved corrosion resistance compared to the base layer without theoverlying anodized dielectric layer. In addition, the anodizing processmay be performed at room temperature (e.g., approximately 25° C. and/orwith no applied heat) and forms the dielectric layers quite quickly.Moreover, in various embodiments the anodizing process is performed as awet chemical process, and thus requires no elevated and/or complicatedheat treatments; advantageously, this prevents phase segregation orcontamination that may accompany processes such as heat treatments orreactive sputtering techniques.

In various embodiments, the composition of the base layer may beengineered to self-limit the anodizing process. For example, theconcentration of the anodizable metallic element(s) within the baselayer may decrease (e.g., gradually or abruptly) as a function ofthickness away from the top surface of the base layer, and may evendiminish to approximately 0% within the thickness of the base layer. Theanodizing process may proceed until substantially all of the anodizablemetallic element(s) have been consumed, at which point the process stopsdue to the anodization resistance of Cu and Mo. For example, the baselayer may be fabricated via a process such as sputtering, in which theprimary element(s) of the layer are co-deposited with the anodizablemetallic element(s). As the layer is deposited, the relativeconcentration (or presence) of one or more of the anodizable metallicelements may be varied within the thickness of the base layer.

In other embodiments, the anodizing process may be self-limiting as aresult of the insulating layer formed on the base layer inhibitingcurrent flow within the layer structure and thereby preventing furtherlayer growth. Thus, the thickness and/or reflectivity of the anodizedlayer may be selected, in various embodiments, via selection of appliedvoltage, assuming that the concentration of anodizable elements withinthe base layer is not prematurely depleted and/or that the anodizedlayer itself is sufficiently free of porosity. In various embodiments,anodization times range from approximately 10 seconds to approximately 5minutes, approximately 10 seconds to approximately 2 minutes,approximately 10 seconds to approximately 1 minute, approximately 10seconds to approximately 50 seconds, or approximately 10 seconds toapproximately 30 seconds. In various embodiments, the base layer may beanodized for a time period longer than these times, even in thesubstantial absence of further layer growth after formation of theanodized layer (and some growth thereof).

In an exemplary implementation, bilayer barriers are formed directly onsubstrate layers such as glass and/or silicon-based layers, andconductor layers including or consisting essentially of highlyconductive metals such as Cu, silver (Ag), aluminum (Al), or gold (Au)(or alloys thereof or alloys containing one or more of these and one ormore other elements) are formed thereover to form the various electrodesin a TFT structure. In another exemplary implementation, highlyconductive metals such as Cu, Ag, Al, and/or Au (or alloys thereof oralloys containing one or more of these and one or more other elements)are utilized as conductive interconnects in a touch-panel display andare capped with bilayer capping layers. In various embodiments, TFTelectrodes may also or instead incorporate bilayer capping layers, andtouch-panel interconnects may also or instead incorporate bilayerbarrier layers.

In various embodiments, the thickness of the bilayer barrier and cappinglayers is, for example, between approximately 15 nm and approximately100 nm. The thickness of the overlying anodized dielectric layer may beselected to obtain one or more optical properties of the layer (e.g.,refractive index, extinction coefficient, etc.) for a desiredapplication. In various embodiments, the thickness of the anodizeddielectric layer (which may include, consist essentially of, or consistof an oxide, e.g., an oxide of one or more of the anodizable elements inthe barrier or capping layer) ranges from approximately 1 nm toapproximately 20 nm, approximately 1 nm to approximately 15 nm,approximately 1 nm to approximately 10 nm, or approximately 1 nm toapproximately 8 nm.

As mentioned above, the bilayer barrier and capping layers protect theunderlying baser layers from corrosion that may occur in, for example,high-humidity and/or high-temperature environments, despite therelatively thin thickness of the anodized dielectric layer. For example,anodized bilayer barrier layers and capping layers may be exposed toenvironments having up to at least approximately 90% humidity and/or atleast 90° C. temperatures without deleterious impact on the resistivityor reflectivity of the layer. The thin thickness of the anodized layeralso presents another advantage, namely that the etch rate of the baselayer is substantially unaffected by the presence of the dielectriclayer, facilitating processing and fabrication of microelectronicdevices without substantial (if any) changes to etch chemistries andprocesses.

In various embodiments, bilayer barrier layers are formed on substratelayers such as glass and/or silicon-based layers to form, withconductive interconnects thereover, the various electrodes in a TFTstructure or to form the metallization in a touch-panel display. Thebase layers of the bilayer capping and/or barrier layers in accordancewith embodiments of the invention may be formed by, e.g., physical vapordeposition techniques such as sputtering from sputtering targets thatinclude, consist essentially of, or consist of the alloy desired for aparticular application. As mentioned above, such base layers may beanodized to form the overlying dielectric layer and thus the finalbilayer structure. In various embodiments, multiple different sputteringtargets, each containing one or more of the elements of the desired baselayer, may be utilized for deposition of the layer.

In an aspect, embodiments of the invention feature a thin-filmtransistor, or another electronic device, that includes, consistsessentially of, or consists of a substrate and an electrode. Theelectrode includes, consists essentially of, or consists of a bilayerbarrier layer and a conductor layer disposed over the barrier layer. Theconductor layer may be disposed in direct mechanical contact with thebarrier layer. The conductor layer includes, consists essentially of, orconsists of Cu, Ag, Al, and/or Au. The conductor layer may include,consist essentially of, or consist of Cu, Ag, and/or Au. The bilayerbarrier layer includes, consists essentially of, or consists of a baselayer and a dielectric layer disposed thereover. The base layerincludes, consists essentially of, or consists of an alloy of Cu and/orMo with one or more anodizable alloying elements selected from the listconsisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. The one or more anodizablealloying elements may be present individually or in combination at aconcentration of 0.5 weight %-50 weight %. The dielectric layerincludes, consists essentially of, or consists of an oxide, nitride, oroxynitride of one or more (or even all) of the one or more anodizablealloying elements.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The substrate may include, consistessentially of, or consist of glass and/or silicon. The substrate mayinclude, consist essentially of, or consist of amorphous silicon. Thebase layer may include, consist essentially of, or consist of an alloyor mixture of (i) Mo and Nb, (ii) Mo, Ta, and Nb, (iii) Mo, Nb, and Ti,(iv) Mo and Ti, or (v) Mo, Nb, and Zr. The base layer may include,consist essentially of, or consist of an alloy or mixture of Cu, Ta, andZr. The dielectric layer may be substantially free of Cu and/or Mo. Thebase layer may include, consist essentially of, or consist of aninterfacial portion disposed beneath the dielectric layer and a bottomportion disposed beneath the interfacial portion. The interfacialportion may be in contact with the dielectric layer. The bottom portionmay be in contact with the interfacial portion. A concentration of atleast one (or even all) of the one or more anodizable alloying elementswithin the interfacial portion may be less than a concentration of atleast one (or even all) of the one or more anodizable alloying elementswithin the bottom portion. The interfacial portion may be substantiallyfree of at least one (or even all) of the one or more anodizablealloying elements. The bottom portion may be substantially free of atleast one (or even all) of the one or more anodizable alloying elements.The electrode may include a bilayer capping layer disposed over theconductor layer. The capping layer may be disposed in contact with theconductor layer. The bilayer capping layer may include, consistessentially of, or consist of a second base layer and a seconddielectric layer disposed thereover. The second base layer may include,consist essentially of, or consist of an alloy of Cu and/or Mo with oneor more second anodizable alloying elements selected from the listconsisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. The one or more secondanodizable alloying elements may be present individually or incombination at a concentration of 0.5 weight %-50 weight %. The seconddielectric layer may include, consist essentially of, or consist of anoxide, nitride, or oxynitride of one or more (or even all) of the one ormore second anodizable alloying elements. The base layer may include,consist essentially of, or consist of an alloy the same as that of thesecond base layer. The base layer may include, consist essentially of,or consist of an alloy different from that of the second base layer.

In another aspect, embodiments of the invention feature a thin-filmtransistor, or other electronic device, that includes, consistsessentially of, or consists of a substrate and an electrode. Theelectrode includes, consists essentially of, or consists of a conductorlayer and a bilayer capping layer disposed over the conductor layer. Thecapping layer may be disposed in direct mechanical contact with theconductor layer. The conductor layer includes, consists essentially of,or consists of Cu, Ag, Al, and/or Au. The conductor layer may include,consist essentially of, or consist of Cu, Ag, and/or Au. The bilayercapping layer includes, consists essentially of, or consists of a baselayer and a dielectric layer disposed thereover. The base layerincludes, consists essentially of, or consists of an alloy of Cu and/orMo with one or more anodizable alloying elements selected from the listconsisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. The one or more anodizablealloying elements may be present individually or in combination at aconcentration of 0.5 weight %-50 weight %. The dielectric layerincludes, consists essentially of, or consists of an oxide, nitride, oroxynitride of one or more (or even all) of the one or more anodizablealloying elements.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The substrate may include, consistessentially of, or consist of glass and/or silicon. The substrate mayinclude, consist essentially of, or consist of amorphous silicon. Thebase layer may include, consist essentially of, or consist of an alloyor mixture of (i) Mo and Nb, (ii) Mo, Ta, and Nb, (iii) Mo, Nb, and Ti,(iv) Mo and Ti, or (v) Mo, Nb, and Zr. The base layer may include,consist essentially of, or consist of an alloy or mixture of Cu, Ta, andZr. The dielectric layer may be substantially free of Cu and/or Mo. Thebase layer may include, consist essentially of, or consist of aninterfacial portion disposed beneath the dielectric layer and a bottomportion disposed beneath the interfacial portion. The interfacialportion may be in contact with the dielectric layer. The bottom portionmay be in contact with the interfacial portion. A concentration of atleast one (or even all) of the one or more anodizable alloying elementswithin the interfacial portion may be less than a concentration of atleast one (or even all) of the one or more anodizable alloying elementswithin the bottom portion. The interfacial portion may be substantiallyfree of at least one (or even all) of the one or more anodizablealloying elements. The bottom portion may be substantially free of atleast one (or even all) of the one or more anodizable alloying elements.

In yet another aspect, embodiments of the invention feature atouch-panel display, or other electronic device, that includes, consistsessentially of, or consists of a substrate and an interconnect disposedthereover. The interconnect comprises, consists essentially of, orconsists of a conductor layer and a bilayer capping layer disposed overthe conductor layer. The capping layer may be disposed in directmechanical contact with the conductor layer. The conductor layerincludes, consists essentially of, or consists of Cu, Ag, Al, and/or Au.The conductor layer may include, consist essentially of, or consist ofCu, Ag, and/or Au. The bilayer capping layer includes, consistsessentially of, or consists of a base layer and a dielectric layerdisposed thereover. The base layer includes, consists essentially of, orconsists of an alloy of Cu and/or Mo with one or more anodizablealloying elements selected from the list consisting of Ta, Nb, Al, Hf,Zr, Ti, and Mg. The one or more anodizable alloying elements may bepresent individually or in combination at a concentration of 0.5 weight%-50 weight %. The dielectric layer includes, consists essentially of,or consists of an oxide, nitride, or oxynitride of one or more (or evenall) of the one or more anodizable alloying elements.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The electronic device may include aplurality of conductive touch-panel row sensors (i) arranged in linesextending along a first direction and (ii) disposed over the substrate.The electronic device may include a plurality of conductive touch-panelcolumn sensors (i) arranged in lines extending along a second directionand intersecting the lines of the row sensors and (ii) disposed over thesubstrate. The interconnect may be disposed at a point of intersectionbetween a line of row sensors and a line of column sensors. Theinterconnect may electrically connect two column sensors or two rowsensors. The interconnect may extend over or under a row sensor andelectrically connect two column sensors. The electronic device mayinclude an insulating layer disposed between the interconnect and therow sensor and electrically insulating the interconnect and the rowsensor. The interconnect may extend over or under a column sensor andelectrically connect two row sensors. The electronic device may includean insulating layer disposed between the interconnect and the columnsensor and electrically insulating the interconnect and the columnsensor. One or more of the row sensors and/or one or more of the columnsensors may include, consist essentially of, or consist of asubstantially transparent conductive material, e.g., indium tin oxide.

The substrate may include, consist essentially of, or consist of aninsulating material. The substrate may include, consist essentially of,or consist of glass. The substrate may include, consist essentially of,or consist of glass and/or silicon. The substrate may include, consistessentially of, or consist of amorphous silicon. The base layer mayinclude, consist essentially of, or consist of an alloy or mixture of(i) Mo and Nb, (ii) Mo, Ta, and Nb, (iii) Mo, Nb, and Ti, (iv) Mo andTi, or (v) Mo, Nb, and Zr. The base layer may include, consistessentially of, or consist of an alloy or mixture of Cu, Ta, and Zr. Thedielectric layer may be substantially free of Cu and/or Mo. The baselayer may include, consist essentially of, or consist of an interfacialportion disposed beneath the dielectric layer and a bottom portiondisposed beneath the interfacial portion. The interfacial portion may bein contact with the dielectric layer. The bottom portion may be incontact with the interfacial portion. A concentration of at least one(or even all) of the one or more anodizable alloying elements within theinterfacial portion may be less than a concentration of at least one (oreven all) of the one or more anodizable alloying elements within thebottom portion. The interfacial portion may be substantially free of atleast one (or even all) of the one or more anodizable alloying elements.The bottom portion may be substantially free of at least one (or evenall) of the one or more anodizable alloying elements.

The interconnect may include a bilayer barrier layer disposed beneaththe conductor layer. The barrier layer may be disposed in contact withthe conductor layer. The bilayer barrier layer may include, consistessentially of, or consist of a second base layer and a seconddielectric layer disposed thereover. The second base layer may include,consist essentially of, or consist of an alloy of Cu and/or Mo with oneor more second anodizable alloying elements selected from the listconsisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. The one or more secondanodizable alloying elements may be present individually or incombination at a concentration of 0.5 weight %-50 weight %. The seconddielectric layer may include, consist essentially of, or consist of anoxide, nitride, or oxynitride of one or more (or even all) of the one ormore second anodizable alloying elements. The base layer may include,consist essentially of, or consist of an alloy the same as that of thesecond base layer. The base layer may include, consist essentially of,or consist of an alloy different from that of the second base layer.

In another aspect, embodiments of the invention feature a touch-paneldisplay, or another electronic device, that includes, consistsessentially of, or consists of a substrate and an interconnect disposedthereover. The interconnect comprises, consists essentially of, orconsists of a conductor layer and a bilayer barrier layer disposedbeneath the conductor layer. The barrier layer may be disposed in directmechanical contact with the conductor layer. The conductor layerincludes, consists essentially of, or consists of Cu, Ag, Al, and/or Au.The conductor layer may include, consist essentially of, or consist ofCu, Ag, and/or Au. The bilayer barrier layer includes, consistsessentially of, or consists of a base layer and a dielectric layerdisposed thereover. The base layer includes, consists essentially of, orconsists of an alloy of Cu and/or Mo with one or more anodizablealloying elements selected from the list consisting of Ta, Nb, Al, Hf,Zr, Ti, and Mg. The one or more anodizable alloying elements may bepresent individually or in combination at a concentration of 0.5 weight%-50 weight %. The dielectric layer includes, consists essentially of,or consists of an oxide, nitride, or oxynitride of one or more (or evenall) of the one or more anodizable alloying elements.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The electronic device may include aplurality of conductive touch-panel row sensors (i) arranged in linesextending along a first direction and (ii) disposed over the substrate.The electronic device may include a plurality of conductive touch-panelcolumn sensors (i) arranged in lines extending along a second directionand intersecting the lines of the row sensors and (ii) disposed over thesubstrate. The interconnect may be disposed at a point of intersectionbetween a line of row sensors and a line of column sensors. Theinterconnect may electrically connect two column sensors or two rowsensors. The interconnect may extend over or under a row sensor andelectrically connect two column sensors. The electronic device mayinclude an insulating layer disposed between the interconnect and therow sensor and electrically insulating the interconnect and the rowsensor. The interconnect may extend over or under a column sensor andelectrically connect two row sensors. The electronic device may includean insulating layer disposed between the interconnect and the columnsensor and electrically insulating the interconnect and the columnsensor. One or more of the row sensors and/or one or more of the columnsensors may include, consist essentially of, or consist of asubstantially transparent conductive material, e.g., indium tin oxide.

The substrate may include, consist essentially of, or consist of aninsulating material. The substrate may include, consist essentially of,or consist of glass. The substrate may include, consist essentially of,or consist of glass and/or silicon. The substrate may include, consistessentially of, or consist of amorphous silicon. The base layer mayinclude, consist essentially of, or consist of an alloy or mixture of(i) Mo and Nb, (ii) Mo, Ta, and Nb, (iii) Mo, Nb, and Ti, (iv) Mo andTi, or (v) Mo, Nb, and Zr. The base layer may include, consistessentially of, or consist of an alloy or mixture of Cu, Ta, and Zr. Thedielectric layer may be substantially free of Cu and/or Mo. The baselayer may include, consist essentially of, or consist of an interfacialportion disposed beneath the dielectric layer and a bottom portiondisposed beneath the interfacial portion. The interfacial portion may bein contact with the dielectric layer. The bottom portion may be incontact with the interfacial portion. A concentration of at least one(or even all) of the one or more anodizable alloying elements within theinterfacial portion may be less than a concentration of at least one (oreven all) of the one or more anodizable alloying elements within thebottom portion. The interfacial portion may be substantially free of atleast one (or even all) of the one or more anodizable alloying elements.The bottom portion may be substantially free of at least one (or evenall) of the one or more anodizable alloying elements.

In yet another aspect, embodiments of the invention feature a method offorming a microelectronic device. A substrate may be provided. A baselayer is deposited over the substrate. The base layer includes, consistsessentially of, or consists of an alloy of Cu and/or Mo with one or moreanodizable alloying elements selected from the list consisting of Ta,Nb, Al, Hf, Zr, Ti, and Mg. The one or more anodizable alloying elementsmay be present individually or in combination at a concentration of 0.5weight %-50 weight %. The base layer is anodized to form a bilayerbarrier layer. The bilayer barrier layer includes, consists essentiallyof, or consists of (i) a dielectric layer and (ii) a remaining portionof the base layer disposed beneath the dielectric layer. A conductorlayer is deposited over the barrier layer.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The dielectric layer may include,consist essentially of, or consist of an oxide, nitride, or oxynitrideof one or more (or even all) of the one or more anodizable alloyingelements. Anodizing the base layer may include, consist essentially of,or consist of immersing at least a portion of the base layer in anelectrolyte and applying a voltage to the base layer (e.g., between thebase layer and an electrode (e.g., a cathode)). The electrolyte mayinclude, consist essentially of, or consist of an acidic solution. Theelectrolyte may include, consist essentially of, or consist of sulfuricacid, nitric acid, chromic acid, and/or phosphoric acid. The electrolytemay include, consist essentially of, or consist of a basic solution. Theelectrolyte may include, consist essentially of, or consist of trisodiumphosphate. Anodizing the base layer may include, consist essentially of,or consist of applying an electrolyte to the base layer while applying avoltage to the electrolyte and/or to the base layer without immersingthe base layer in the electrolyte. The electrolyte may be applied to thebase layer using a brush electrode. The base layer may be anodized atroom temperature.

A mask layer may be formed or disposed over the conductor layer. Themask layer may include, consist essentially of, or consist ofphotoresist, an oxide layer, a nitride layer, and/or an oxynitridelayer. The mask layer may be patterned to reveal a portion of theconductor layer. A remaining portion of the mask layer may at leastpartially define a shape of an electrode. Thereafter, portions of theconductor layer and the bilayer barrier layer not masked by thepatterned mask layer may be removed. A second base layer may bedeposited over at least a portion of the conductor layer. The secondbase layer may include, consist essentially of, or consist of an alloyof Cu and/or Mo with one or more second anodizable alloying elementsselected from the list consisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. Theone or more second anodizable alloying elements may be presentindividually or in combination at a concentration of 0.5 weight %-50weight %. The second base layer may be anodized to form a bilayercapping layer. The bilayer capping layer may include, consistessentially of, or consist of (i) a second dielectric layer and (ii) aremaining portion of the second base layer disposed beneath the seconddielectric layer. The second dielectric layer may include, consistessentially of, or consist of an oxide, nitride, or oxynitride of one ormore (or even all) of the one or more second anodizable alloyingelements. The base layer may include, consist essentially of, or consistof an alloy the same as that of the second base layer. The base layermay include, consist essentially of, or consist of an alloy differentfrom that of the second base layer.

In another aspect, embodiments of the invention feature a method offorming an interconnect of a touch-panel display. The method includesproviding structure including consisting essentially of, or consistingof (i) a substrate, (ii) a plurality of conductive touch-panel rowsensors (a) arranged in lines extending along a first direction and (b)disposed over the substrate, and (iii) a plurality of conductivetouch-panel column sensors (a) arranged in lines extending along asecond direction and intersecting the lines of the row sensors and (b)disposed over the substrate. An insulator layer is deposited or formedat least at a point of intersection between a line of row sensors and aline of column sensors. A conductor layer is deposited or formed overthe insulator layer. The conductor layer may be in direct mechanicalcontact with the insulator layer. A base layer is deposited or formedover the conductor layer. The base layer includes, consists essentiallyof, or consists of an alloy of Cu and/or Mo with one or more anodizablealloying elements selected from the list consisting of Ta, Nb, Al, Hf,Zr, Ti, and Mg. The one or more anodizable alloying elements may bepresent individually or in combination at a concentration of 0.5 weight%-50 weight %. The base layer is anodized to form a bilayer cappinglayer. The bilayer capping layer includes, consists essentially of, orconsists of (i) a dielectric layer and (ii) a remaining portion of thebase layer disposed beneath the dielectric layer. A mask layer is formedor deposited over the bilayer capping layer. The mask layer is patternedto reveal a portion of the bilayer capping layer, a remaining portion ofthe mask layer at least partially defining a shape of the interconnect.After the mask layer is patterned, portions of the bilayer capping layerand the conductor layer not masked by the patterned mask layer areremoved.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The dielectric layer may include,consist essentially of, or consist of an oxide, nitride, or oxynitrideof one or more (or even all) of the one or more anodizable alloyingelements. Anodizing the base layer may include, consist essentially of,or consist of immersing at least a portion of the base layer in anelectrolyte and applying a voltage to the base layer (e.g., between thebase layer and an electrode (e.g., a cathode)). The electrolyte mayinclude, consist essentially of, or consist of an acidic solution. Theelectrolyte may include, consist essentially of, or consist of sulfuricacid, nitric acid, chromic acid, and/or phosphoric acid. The electrolytemay include, consist essentially of, or consist of a basic solution. Theelectrolyte may include, consist essentially of, or consist of trisodiumphosphate. Anodizing the base layer may include, consist essentially of,or consist of applying an electrolyte to the base layer while applying avoltage to the electrolyte and/or to the base layer without immersingthe base layer in the electrolyte. The electrolyte may be applied to thebase layer using a brush electrode. The base layer may be anodized atroom temperature.

In yet another aspect, embodiments of the invention feature a method offorming a bilayer capping layer for a metallic feature of an electronicdevice. A conductor layer is formed or deposited over a substrate. Theconductor layer may be in direct mechanical contact with the substrate.A base layer is deposited or formed over the conductor layer. The baselayer may be in direct mechanical contact with the conductor layer. Thebase layer includes, consists essentially of, or consists of an alloy ofCu and/or Mo with one or more anodizable alloying elements selected fromthe list consisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg. The one or moreanodizable alloying elements may be present individually or incombination at a concentration of 0.5 weight %-50 weight %. The baselayer is anodized to form a bilayer capping layer. The bilayer cappinglayer includes, consists essentially of, or consists of (i) a dielectriclayer and (ii) a remaining portion of the base layer disposed beneaththe dielectric layer.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The dielectric layer may include,consist essentially of, or consist of an oxide, nitride, or oxynitrideof one or more (or even all) of the one or more anodizable alloyingelements. Anodizing the base layer may include, consist essentially of,or consist of immersing at least a portion of the base layer in anelectrolyte and applying a voltage to the base layer (e.g., between thebase layer and an electrode (e.g., a cathode)). The electrolyte mayinclude, consist essentially of, or consist of an acidic solution. Theelectrolyte may include, consist essentially of, or consist of sulfuricacid, nitric acid, chromic acid, and/or phosphoric acid. The electrolytemay include, consist essentially of, or consist of a basic solution. Theelectrolyte may include, consist essentially of, or consist of trisodiumphosphate. Anodizing the base layer may include, consist essentially of,or consist of applying an electrolyte to the base layer while applying avoltage to the electrolyte and/or to the base layer without immersingthe base layer in the electrolyte. The electrolyte may be applied to thebase layer using a brush electrode. The base layer may be anodized atroom temperature.

These and other objects, along with advantages and features of thepresent invention herein disclosed, will become more apparent throughreference to the following description, the accompanying drawings, andthe claims. Furthermore, it is to be understood that the features of thevarious embodiments described herein are not mutually exclusive and mayexist in various combinations and permutations. As used herein, theterms “approximately,” “about,” and “substantially” mean ±10%, and insome embodiments, ±5%. The term “consists essentially of” meansexcluding other materials that contribute to function, unless otherwisedefined herein. Nonetheless, such other materials may be present,collectively or individually, in trace amounts. For example, a structureconsisting essentially of multiple metals will generally include onlythose metals and only unintentional impurities (which may be metallic ornon-metallic) that may be detectable via chemical analysis but do notcontribute to function. As used herein, “consisting essentially of atleast one metal” refers to a metal or a mixture of two or more metalsbut not compounds between a metal and a non-metallic element or chemicalspecies such as oxygen or nitrogen (e.g., metal nitrides or metaloxides); such non-metallic elements or chemical species may be present,collectively or individually, in trace amounts, e.g., as impurities. Asused herein, “columns” and “rows” refer to elements arranged indifferent directions (and that may intersect), and are otherwisearbitrary unless otherwise noted; i.e., an arrangement of elements maybe a row or a column, regardless of its orientation in space or within adevice. As used herein, “substrate” or “base layer” refers to a supportmember (e.g., a semiconductor substrate such as silicon, GaAs, GaN, SiC,sapphire, or InP, or a platform including or consisting essentially ofanother material, e.g., an insulating material such as glass) with orwithout one or more additional layers disposed thereon, or to the one ormore additional layers themselves.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings, like reference characters generally refer to the sameparts throughout the different views. Also, the drawings are notnecessarily to scale, emphasis instead generally being placed uponillustrating the principles of the invention. In the followingdescription, various embodiments of the present invention are describedwith reference to the following drawings, in which:

FIG. 1 is a schematic cross-section of a thin-film transistor for aliquid crystal display;

FIG. 2A is a plan-view schematic of the sensor array of a touch-paneldisplay;

FIG. 2B is a magnified perspective view of a portion of the sensor arrayof FIG. 2A;

FIG. 2C is a schematic cross-section of the sensor-array portion of FIG.2B;

FIGS. 3A-3D are schematic cross-sections of a TFT electrode duringfabrication in accordance with various embodiments of the invention;

FIGS. 4A-4C are schematic cross-sections of an interconnect for atouch-panel display during fabrication in accordance with variousembodiments of the invention;

FIG. 5 is a schematic of an apparatus utilized for anodization inaccordance with various embodiments of the invention;

FIG. 6 is a graph of reflectivity of a layer, as a function ofwavelength, before anodization and after anodization at two differentapplied voltages in accordance with various embodiments of theinvention;

FIG. 7 is a graph of reflectivity of a layer, as a function ofwavelength, before and after anodization in accordance with variousembodiments of the invention;

FIG. 8 is a graph of reflectivity of a layer, as a function ofwavelength, before and after anodization in accordance with variousembodiments of the invention;

FIG. 9 is a graph of reflectivity of a layer, as a function ofwavelength, before and after anodization in accordance with variousembodiments of the invention;

FIG. 10 is a graph of reflectivity of a layer, as a function ofwavelength, before and after brush anodization in accordance withvarious embodiments of the invention;

FIG. 11A is a graph of reflectivity, as a function of wavelength, of anon-anodized layer before and after exposure to a corrosive medium;

FIG. 11B is a graph of reflectivity, as a function of wavelength, of alayer anodized in accordance with various embodiments of the inventionbefore and after exposure to a corrosive medium;

FIG. 12 is a series of images of the layer of FIG. 11B before and duringcorrosion testing;

FIG. 13 is a graph of sheet resistance of two different layers anodizedin accordance with various embodiments of the invention as a function oftime during corrosion testing;

FIG. 14 is a graph comparing the surface chemistry of an oxidizednon-anodized layer with that of a layer anodized in accordance withvarious embodiments of the invention;

FIG. 15 is a graph of reflectivity of a layer, as a function ofwavelength, before and after anodization in accordance with variousembodiments of the invention;

FIG. 16 is a graph of reflectivity of a layer, as a function ofwavelength, before and after anodization in accordance with variousembodiments of the invention; and

FIG. 17 is a graph of reflectivity of a layer, as a function ofwavelength, as a function of applied anodization voltage in accordancewith various embodiments of the invention.

DETAILED DESCRIPTION

FIG. 3A depicts an initial step in the fabrication of a TFT gateelectrode in accordance with embodiments of the present invention. Asshown, a base layer 300 is deposited on a substrate 310 (e.g., a glassor silicon substrate) by, e.g., sputtering, co-sputtering (i.e., fromtwo or more elemental-metal sputtering targets) or other physicaldeposition process. In various embodiments, the base layer 300 includes,consists essentially of, or consists of an alloy of Cu and/or Mo (and/orother non-anodizable metal) with up to 20%, or even up to 50%, (and atleast, e.g., 0.5% or 1%) of one or more anodizable metallic elements(e.g., Ta, Nb, Al, Hf, Zr, Ti, and/or Mg). As shown in FIG. 3B, the baselayer 300 is then anodized to form a bilayer barrier layer 320 composedof the remaining portion of the base layer 300 and an overlyingdielectric layer 330 that includes, consists essentially of, or consistsof an oxide and/or nitride of the one or more alloying elements. SinceCu and Mo are typically not anodizable, the dielectric layer 330 may besubstantially free of Cu and Mo. In addition, an interfacial region ofthe base layer 300 (i.e., the portion of the base layer directlyunderlying and in contact with the dielectric layer) may be depleted in,or may even be substantially free of, the anodizable metallicelement(s), which may be preferentially “consumed” in the anodizingprocess. This interfacial region of the base layer 300 may have athickness of, for example, 1 nm-20 nm. Rather than being fully depletedin the alloying elements, the interfacial region may contain one or moreof the alloying elements but in a concentration that decreases towardthe dielectric layer 330.

As shown in FIG. 3C, a conductor layer 340 may be deposited on thebarrier layer 320 by, e.g., sputtering or other physical depositionprocess. The conductor layer 340 may include, consist essentially of, orconsist of a highly conductive metal such as, for example, Cu, Ag, Al,and/or Au, or an alloy or mixture containing two or more of these metalsor one or more of these metals with one or more other elements (e.g.,other metals). In various embodiments, the conductor layer 340 is notanodizable (i.e., does not form a dielectric layer of any appreciable ordetectable thickness upon subjection to an electrochemical anodizationprocess or forms a dielectric layer that is unstable, not corrosionresistant, and/or that is easily mechanically removed; for example,while ferrous metals (i.e., metals comprising, consisting essentiallyof, or consisting of iron) oxidize, the resulting dielectric layer isoften unstable and may easily flake off). Typically the thickness of thebarrier layer 320 will be between approximately 5% and approximately 25%(e.g., approximately 10%) of the thickness of conductor layer 340. Theconductor layer 340 and the barrier layer 320 may be subsequentlypatterned by conventional photolithography processes to form a gateelectrode 350, as shown in FIG. 3D. For example, a mask layer (e.g.,photoresist) may be formed over the conductor layer, the mask layer maybe patterned, and the unmasked areas of the conductor layer 340 and thebarrier layer 320 may be removed via, e.g., wet or dry etching.

FIG. 4A depicts an initial step in the fabrication of a touch-panelsensor interconnect in accordance with embodiments of the presentinvention. As shown, a conductor layer 400 is deposited over a sensor410 (e.g., a row or column sensor that may include, consist essentiallyof, or consist of, e.g., a transparent conductor such as ITO) on asubstrate 420 (e.g., a glass or silicon substrate) by, e.g., sputteringor other physical deposition process. A base layer 430 is subsequentlydeposited on the conductive layer 400 by, e.g., sputtering,co-sputtering, or other physical deposition process. In variousembodiments, the base layer 430 includes, consists essentially of, orconsists of an alloy of Cu and/or Mo (and/or other non-anodizable metal)with up to 20%, or even up to 50%, of one or more anodizable metallicelements (e.g., Ta, Nb, Al, Hf, Zr, Ti, and/or Mg). The conductor layer400 may include, consist essentially of, or consist of a highlyconductive metal such as, for example, Cu, Ag, Al, and/or Au, or analloy or mixture containing two or more of these metals or one or moreof these metals with one or more other elements (e.g., other metals). Invarious embodiments, the conductor layer 400 is not anodizable.

As shown in FIG. 4B, the base layer 430 is then anodized to form abilayer capping layer 440 composed of the remaining portion of the baselayer 430 and an overlying dielectric layer 450 that includes, consistsessentially of, or consists of an oxide and/or nitride of the one ormore alloying elements. Since Cu and Mo are typically not anodizable,the dielectric layer 450 may be substantially free of Cu and Mo (e.g.,containing less than approximately 5%, or even less than approximately1%, Cu and Mo). In addition, an interfacial region of the base layer 430(i.e., the portion of the base layer directly underlying and in contactwith the dielectric layer) may be depleted in, or may even besubstantially free of, the anodizable metallic element(s), which may bepreferentially “consumed” in the anodizing process. This interfacialregion of the base layer 430 may have a thickness of, for example, 1nm-20 nm. Rather than being fully depleted in the alloying elements, theinterfacial region may contain one or more of the alloying elements butin a concentration that decreases toward the dielectric layer 450.

As shown in FIG. 4C, the capping layer 440 and the conductor layer 400may be subsequently patterned by conventional photolithography processesto form an interconnect 460. For example, a mask layer (e.g.,photoresist) may be formed over the capping layer 440, the mask layermay be patterned, and the unmasked areas of the capping layer 440 andconductor layer 400 may be removed via, e.g., wet or dry etching.

In various embodiments, the conductor layer 400 is not anodizable (e.g.,consists essentially or consists of Cu), and the base layer 430 isanodized after patterning of the interconnect 460. In such embodiments,the base layer 430 and conductor layer 400 may be patterned as describedabove, and then the base layer 430 is anodized to form the overlyingdielectric layer 450. Since the conductor layer 400 is not anodizable,it is not affected by the anodization process, and only exposed regionsof the base layer 430 are anodized to form overlying dielectric layers450.

FIG. 5 depicts a schematic of an apparatus 500 for the anodizing of thebase layer in accordance with embodiments of the present invention. Asshown, a base layer 510 and a cathode material 520 are immersed in anelectrolyte 530 and electrically coupled to a power supply 540. Thecathode 520 may include, consist essentially of, or consist of, e.g.,Pt, Al, Pb, or Ta. Upon application of a voltage by power supply 540,current flows through the electrolyte 530, leading to formation of adielectric layer on the base layer 510. For example, oxygen and/ornitrogen may be liberated from the electrolyte and react with the one ormore alloying elements within the base layer 510 to form the dielectriclayer. In various embodiments, hydrogen and/or one or more other gaseousby-products are produced at the cathode 520. The thickness of theresulting dielectric layer may be controlled by, e.g., varying thevoltage applied by the power supply 540. The electrolyte 530 mayinclude, consist essentially or, or consist of one or more acidicsolutions such as sulfuric acid, nitric acid, chromic acid, orphosphoric acid. In other embodiments, the electrolyte 530 may include,consist essentially of, or consist of one or more basic solutions suchas aqueous sodium phosphate (e.g., trisodium phosphate). In general, theelectrolyte 530 has a pH greater than or lower than 7. For example, thepH of the electrolyte 530 may be 6 or less (e.g., between 0 and 6, orbetween 1 and 6, or between 0 and 5, or between 0 and 4, or between 0and 3), or the pH of the electrolyte 530 may be 8 or more (e.g., between8 and 14, or between 8 and 13, or between 9 and 14, or between 10 and14) Even though the electrolyte 530 may be acidic, in variousembodiments of the invention the only portion of the base layer consumedin the anodization process is the portion oxidized and/or nitrided toform the dielectric layer—i.e., the base layer is not otherwise etchedor patterned during the anodizing process. The anodizing process may beperformed as a batch (i.e., multiple-substrate) process or as asingle-substrate process. Advantageously, the anodizing process inembodiments of the present invention may be performed at roomtemperature (e.g., approximately 25° C.), thereby enabling formation ofanodized dielectric layers (and thus bilayer capping and/or barrierlayers) even on substrates containing heat-sensitive elements.

In various embodiments of the invention, the base layer 510 may beanodized without immersion in the electrolyte 530. For example, theelectrolyte 530 may be applied to all or a portion of the surface of thebase layer 510 (e.g., with a brush electrode and/or by spraying) whilevoltage is applied to the electrolyte 530 (e.g., via a power sourceconnected to the brush electrode) and/or the base layer 510.

Bilayer barrier layers and capping layers in accordance with variousembodiments of the invention exhibit advantageously low reflectivity,particularly when compared to their base layer constituents alone. FIG.6 is a graph of reflectivity as a function of wavelength for a 100nm-thick film of 90% Mo and 10% Nb disposed on a silicon substratebefore anodization (reflectivity 600) and after anodization at twodifferent applied voltages (and thus two different thicknesses of theresulting dielectric layer) of 2.2V (reflectivity 610) and 3.0V(reflectivity 620) in a solution of trisodium phosphate (TSP) and waterhaving a pH of approximately 11. As shown, the formation of theoverlying dielectric layer reduces the reflectivity of the layer from58%-70% to 28%-60% (2.2V) to 8%-30% (3.0V). These and all otherreflectivity measurements reported herein were performed utilizing aCary 50 UV-Vis Spectrophotometer available from Varian, Inc. of PaloAlto, Calif. This system is equipped with a dual-beam, Czerny-Turnermonochromator capable of measuring 190-1100 nm wavelength range, havingapproximately 1.5 nm fixed spectral bandwidth, and utilizing afull-spectrum Xe pulse lamp single source. The system was calibratedwith the supplied highly reflective (˜100%) calibration sample prior toeach measurement. The reflectivity data shown in FIG. 6 (and otherfigures herewith) are plotted without any post-processing. Theanodizations performed in accordance with the examples presented hereinwere performed for times ranging from approximately 10 seconds toapproximately 50 seconds unless otherwise indicated, although increasedanodization time would, in general, have little if any impact on theresulting anodized layers or their properties (e.g., reflectivity).

FIG. 7 is a similar graph of reflectivity as a function of wavelengthfor a 100 nm-thick film of 91% Mo, 6% Nb, and 3% Ta on a siliconsubstrate before anodization (reflectivity 700) and after anodization atan applied voltage of 20V (reflectivity 710) in a solution of TSP andwater having a pH of approximately 11. As shown, the formation of theoverlying dielectric layer reduces the reflectivity of the layer from62%-70% to 35%-45%. FIG. 8 is another graph of reflectivity as afunction of wavelength for a 100 nm-thick film of 85% Mo, 10% Nb, and 5%Ti on a silicon substrate before anodization (reflectivity 800) andafter anodization (reflectivity 810) in a solution of TSP and waterhaving a pH of approximately 11. As shown, the formation of theoverlying dielectric layer reduces the reflectivity of the layer from30%-48% to 18%-45%.

FIG. 9 is a graph of reflectivity as a function of wavelength for a 50nm-thick film of 91% Cu, 4% Ta, and 5% Zr atop a 300 nm-thick layer ofCu on a Si substrate before anodization (reflectivity 900) and afteranodization at two different applied voltages (and thus two differentthicknesses of the resulting dielectric layer) of 5V (reflectivity 910)and 7V (reflectivity 920) in a solution of phosphoric acid and waterhaving a pH of approximately 4. As shown, the formation of the overlyingdielectric layer reduces the reflectivity of the layer from 53%-92% to22%-52% (5V) to 15%-22% (7V).

As discussed herein, layers may be anodized in accordance withembodiments of the present invention without immersion in theelectrolyte. FIG. 10 is a graph of reflectivity as a function ofwavelength for a 100 nm-thick film of 90% Mo and 10% Nb disposed on aglass substrate before anodization (reflectivity 1000) and afteranodization (reflectivity 1010) utilizing a brush electrode and anelectrolyte of TSP and water having a pH of approximately 11. As shown,the formation of the overlying dielectric layer reduces the reflectivityof the layer from 68%-70% to 2%-35%.

Bilayer capping and barrier layers in accordance with embodiments of theinvention also advantageously exhibit stable reflectivity even afterexposure to corrosive environments. MoNb (10% Nb) base layers weresubjected to a corrosion test in which the non-anodized base layers wereexposed to a temperature of 85° C. and humidity of 85% for a period offour weeks. As shown in FIG. 11A, the reflectivity of the bare baselayer prior to the corrosion test (reflectivity 1100) decreaseddramatically by 40% or more after the corrosion test (reflectivity1110). In contrast, the bilayer sample exhibited substantially the samereflectivity both before (reflectivity 1120) and after the corrosiontest (reflectivity 1130), as shown in FIG. 11B. Furthermore, as shown inFIG. 12, the bilayer sample was defect-free upon visual inspection afterboth three weeks and four weeks of corrosion testing. FIG. 13 is a graphof sheet resistance of two different anodized layers, 91% Mo, 6% Nb, and3% Ta (sheet resistance 1300), and 90% Mo and 10% Nb (sheet resistance1310) as a function of time during a corrosion test involving exposureto a temperature of 85° C. and humidity of 85%. As shown, even after aperiod of 40 days, the sheet resistance of both samples is substantiallythe same as on day zero when the test began.

FIG. 14 is a comparison of surface chemistry measured using x-rayphotoelectron spectroscopy (XPS) for two different layers, each layerbeing initially composed of 90% Mo and 10% Nb. Sample 1400 was annealedwithout anodization in air at a temperature of 350° C. for 30 minutes,which resulted in the formation of a Mo oxide thereover. Such a Mo oxidelayer is not resistant to corrosion, as shown in FIG. 11A. In contrast,sample 1410 was anodized in a solution of TSP and water having a pH ofapproximately 11. As shown in FIG. 14, the anodized sample 1410 containsa larger amount of Nb on the surface compared to the annealed sample1400, indicating that the dielectric layer on the surface of theanodized sample 1410 is based on Nb rather than Mo. As shown in FIG.11B, such an anodized layer is much more resistant to corrosion.

Advantageously, dielectric layers formed by anodization in accordancewith embodiments of the present invention also do not deleteriouslyimpact the etching behavior of the underlying base layer, therebyfacilitating the processing of anodized layers for use as capping layersand barrier layers. FIG. 15 graph of reflectivity as a function ofwavelength for a 100 nm-thick film of 85% Mo, 10% Nb, and 5% Zr on asilicon substrate before anodization (reflectivity 1500) and afteranodization (reflectivity 1510) at an applied voltage of 5V in asolution of TSP and water having a pH of approximately 11. As shown, theformation of the overlying dielectric layer reduces the reflectivity ofthe layer from 65%-70% to 20%-35%. Etching studies were performed on (1)the unanodized MoNbZr layer, (2) the same layer having been annealed inair at 350° C. for 15 minutes, thereby forming a Mo oxide thereover, and(3) the anodized MoNbZr layer. Each of the layers was etched in amixture of phosphoric acid, acetic acid, and nitric acid (a “PAN”etchant) at a temperature of 42° C., and the etch rate was measured. Theunanodized and unannealed layer etched at a rate of 34 ↑/s, and theanodized layer etched at a rate of 33 Å/s; since the etch rates aresubstantially identical, this indicates that anodized layers may beincorporated into conventional fabrication processes with little if anychanges required in etching and other processing steps. In contrast, theannealed sample was not measurably etched after a period of more than600 seconds, indicating that such Mo oxide layers not only do not resistcorrosion as well as anodized layers in accordance with embodiments ofthe invention but also cannot be etched using etch processes utilizedfor the untreated base layers.

FIG. 16 is a graph of reflectivity as a function of wavelength for a 250nm-thick film of 50% Mo and 50% Ti on a silicon substrate beforeanodization (reflectivity 1600) and after anodization (reflectivity1610) at an applied voltage of 12 in a solution of TSP and water havinga pH of approximately 11. As shown, the formation of the overlyingdielectric layer (which has a thickness of approximately 1.5 nm) reducesthe reflectivity of the layer from 60%-68% to 8%-40%. FIG. 17 is a graphdepicting the reflectivity of the anodized film as a function of appliedvoltage, from 0V (i.e., not anodized) to 12V, demonstrating that highervoltage (and thus a thicker anodized dielectric layer) results in lowerreflectivity. Moreover, the thickness of the anodized dielectric layer,as well as the reflectivity thereof, may be selected via adjustment ofthe anodization voltage.

The terms and expressions employed herein are used as terms andexpressions of description and not of limitation, and there is nointention, in the use of such terms and expressions, of excluding anyequivalents of the features shown and described or portions thereof. Inaddition, having described certain embodiments of the invention, it willbe apparent to those of ordinary skill in the art that other embodimentsincorporating the concepts disclosed herein may be used withoutdeparting from the spirit and scope of the invention. Accordingly, thedescribed embodiments are to be considered in all respects as onlyillustrative and not restrictive.

What is claimed is:
 1. A method of forming a microelectronic device, themethod comprising: providing a substrate; depositing over the substratea base layer comprising an alloy of Cu and/or Mo with 0.5 weight %-50weight % of one or more anodizable alloying elements selected from thelist consisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg; anodizing the baselayer to form a bilayer barrier layer comprising (i) a dielectric layerand (ii) a remaining portion of the base layer disposed beneath thedielectric layer; and depositing a conductor layer over the barrierlayer, wherein anodizing the base layer comprises applying anelectrolyte to the base layer while applying a voltage thereto withoutimmersing the base layer in the electrolyte.
 2. The method of claim 1,wherein the dielectric layer comprises an oxide, nitride, or oxynitrideof the one or more anodizable alloying elements.
 3. The method of claim1, wherein the electrolyte is applied to the base layer using a brushelectrode.
 4. The method of claim 1, further comprising: forming a masklayer over the conductor layer; patterning the mask layer to reveal aportion of the conductor layer, a remaining portion of the mask layer atleast partially defining a shape of an electrode; and thereafter,removing portions of the conductor layer and the bilayer barrier layernot masked by the patterned mask layer.
 5. The method of claim 1,wherein the electrolyte comprises an acidic solution.
 6. The method ofclaim 1, wherein the electrolyte comprises sulfuric acid, nitric acid,chromic acid, and/or phosphoric acid.
 7. The method of claim 1, whereinthe electrolyte comprises a basic solution.
 8. The method of claim 1,wherein the electrolyte comprises trisodium phosphate.
 9. The method ofclaim 1, further comprising: depositing over at least a portion of theconductor layer a second base layer comprising an alloy of Cu and/or Mowith 0.5 weight %-50 weight % of one or more second anodizable alloyingelements selected from the list consisting of Ta, Nb, Al, Hf, Zr, Ti,and Mg; and anodizing the second base layer to form a bilayer cappinglayer comprising (i) a second dielectric layer and (ii) a remainingportion of the second base layer disposed beneath the second dielectriclayer.
 10. The method of claim 9, wherein the base layer comprises analloy the same as that of the second base layer.
 11. The method of claim9, wherein the base layer comprises an alloy different from that of thesecond base layer.
 12. The method of claim 9, wherein the seconddielectric layer comprises an oxide, nitride, or oxynitride of the oneor more second anodizable alloying elements.
 13. A method of forming amicroelectronic device, the method comprising: providing a substrate;depositing over the substrate a base layer comprising an alloy of Cuand/or Mo with 0.5 weight %-50 weight % of one or more anodizablealloying elements selected from the list consisting of Ta, Nb, Al, Hf,Zr, Ti, and Mg; anodizing the base layer to form a bilayer barrier layercomprising (i) a dielectric layer and (ii) a remaining portion of thebase layer disposed beneath the dielectric layer; and depositing aconductor layer over the barrier layer, wherein anodizing the base layercomprises: immersing the base layer in an electrolyte; and applying avoltage between the base layer and a cathode.
 14. The method of claim13, wherein the electrolyte comprises an acidic solution.
 15. The methodof claim 13, wherein the electrolyte comprises sulfuric acid, nitricacid, chromic acid, and/or phosphoric acid.
 16. The method of claim 13,wherein the electrolyte comprises a basic solution.
 17. The method ofclaim 13, wherein the electrolyte comprises trisodium phosphate.
 18. Themethod of claim 13, wherein the dielectric layer comprises an oxide,nitride, or oxynitride of the one or more anodizable alloying elements.19. The method of claim 13, further comprising: forming a mask layerover the conductor layer; patterning the mask layer to reveal a portionof the conductor layer, a remaining portion of the mask layer at leastpartially defining a shape of an electrode; and thereafter, removingportions of the conductor layer and the bilayer barrier layer not maskedby the patterned mask layer.
 20. The method of claim 13, furthercomprising: depositing over at least a portion of the conductor layer asecond base layer comprising an alloy of Cu and/or Mo with 0.5 weight%-50 weight % of one or more second anodizable alloying elementsselected from the list consisting of Ta, Nb, Al, Hf, Zr, Ti, and Mg; andanodizing the second base layer to form a bilayer capping layercomprising (i) a second dielectric layer and (ii) a remaining portion ofthe second base layer disposed beneath the second dielectric layer. 21.The method of claim 20, wherein the base layer comprises an alloy thesame as that of the second base layer.
 22. The method of claim 20,wherein the base layer comprises an alloy different from that of thesecond base layer.
 23. The method of claim 20, wherein the seconddielectric layer comprises an oxide, nitride, or oxynitride of the oneor more second anodizable alloying elements.
 24. A method of forming amicroelectronic device, the method comprising: providing a substrate;depositing over the substrate a base layer comprising an alloy of Cuand/or Mo with 0.5 weight %-50 weight % of one or more anodizablealloying elements selected from the list consisting of Ta, Nb, Al, Hf,Zr, Ti, and Mg; anodizing the base layer to form a bilayer barrier layercomprising (i) a dielectric layer and (ii) a remaining portion of thebase layer disposed beneath the dielectric layer; and depositing aconductor layer over the barrier layer, wherein the base layer isanodized at room temperature.
 25. The method of claim 24, wherein thedielectric layer comprises an oxide, nitride, or oxynitride of the oneor more anodizable alloying elements.
 26. The method of claim 24,further comprising: forming a mask layer over the conductor layer;patterning the mask layer to reveal a portion of the conductor layer, aremaining portion of the mask layer at least partially defining a shapeof an electrode; and thereafter, removing portions of the conductorlayer and the bilayer barrier layer not masked by the patterned masklayer.
 27. The method of claim 24, further comprising: depositing overat least a portion of the conductor layer a second base layer comprisingan alloy of Cu and/or Mo with 0.5 weight %-50 weight % of one or moresecond anodizable alloying elements selected from the list consisting ofTa, Nb, Al, Hf, Zr, Ti, and Mg; and anodizing the second base layer toform a bilayer capping layer comprising (i) a second dielectric layerand (ii) a remaining portion of the second base layer disposed beneaththe second dielectric layer.
 28. The method of claim 27, wherein thebase layer comprises an alloy the same as that of the second base layer.29. The method of claim 27, wherein the base layer comprises an alloydifferent from that of the second base layer.
 30. The method of claim27, wherein the second dielectric layer comprises an oxide, nitride, oroxynitride of the one or more second anodizable alloying elements.